The subject-matter of the invention is a composition for the oxidation dyeing of keratinous fibres, in particular of human keratinous fibres, such as hair, comprising at least one suitably selected para-phenylenediamine derivative as oxidation base, in combination with at least one suitably selected coupler of meta-aminophenol or meta-diphenol type, and the dyeing process employing this composition.
It is known to dye keratinous fibres and in particular human hair with dyeing compositions comprising oxidation dye precursors, in particular ortho- or para-phenylenediamines or ortho- or para-aminophenols, generally known as oxidation bases. Oxidation dye precursors or oxidation bases are colourless or weakly coloured compounds which, in combination with oxidizing substances, can give rise by an oxidative coupling process to coloured and colouring compounds.
It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or colouring modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols or meta-diphenols.
The variety of the molecules employed as oxidation bases and couplers makes it possible to obtain a rich palette of colours.
The so-called xe2x80x9cpermanentxe2x80x9d colouring obtained by virtue of these oxidation dyes has, however, to satisfy a certain number of requirements. Thus, it must be without disadvantage toxicologically and it must make it possible to obtain shades with the desired intensity and behave well in the face of external agents (light, bad weather, washing, permanent waving, perspiration or rubbing).
Provision has already been made, in particular in French Patent Application FR-A-2 364 888, for compositions for the oxidation dyeing of keratinous fibres comprising, as oxidation base, para-phenylenediamines substituted in the 2 position, such as, for example, 2-(xcex2-mesylaminoethyloxy)-para-phenylenediamine, optionally in combination with one or more couplers of meta-aminophenol, such as, for example, 5-amino-2-methylphenol, meta-phenylenediamine or meta-diphenol type, in order to obtain, in oxidizing alkaline medium, colourings with blue shades which are more or less purple, these being very luminous. The colourings obtained with these compositions are not, however, entirely satisfactory, in particular as regards the behaviour of these colourings with respect to various attacks which hair may be subjected to and in particular with respect to perspiration and permanent waving.
The present invention is targeted at providing novel compositions for the oxidation dyeing of keratinous fibres and in particular of human keratinous fibres, such as hair, which exhibit very good dyeing properties.
Thus, the Applicant Company has now just discovered that it is possible to obtain novel dyes which are particularly resistant and which generate intense colourings by combining:
at least one para-phenylenediamine derivative of formula (I) defined below and/or one of its addition salts with an acid,
at least coupler of formula (II) defined below and/or one of its addition salts with an acid.
This discovery is at the basis of the present invention.
The first subject-matter of the invention is therefore a composition for the oxidation dyeing of keratinous fibres and in particular of human keratinous fibres, such as hair, characterized in that it comprises, in a medium appropriate for dyeing:
at least one oxidation base chosen from para-phenylenediamine derivatives of following formula (I) and their addition salts with an acid: 
xe2x80x83in which:
R1 represents a hydrogen atom or a mesyl, carbamoyl or acetyl radical,
n is an integer between 1 and 4 inclusive;
at least one coupler chosen from compounds of following formula (II) and their addition salts with an acid: 
xe2x80x83in which:
R2 represents a hydroxyl radical or an NHR4 group where R4 denotes a hydrogen atom or a C1-C4 alkyl, C1-C4 monohydroxyalkyl or C2-C4 polyhydroxyalkyl radical,
R3 represents a hydrogen atom, a C1-C4 alkyl or C1-C4 alkoxy radical or a halogen atom chosen from chlorine, bromine and fluorine;
it being understood that, when n=2, when R1 represents a mesyl radical, when R3 represents a methyl radical in the 6 position and when R2 represents an NHR4 group, then R4 is other than a hydrogen atom.
The colourings obtained with the above compositions exhibit a good dyeing power and excellent properties of resistance both with respect to atmospheric agents, such as light and bad weather, and with respect to perspiration and various treatments which hair can be subjected to (shampoos, permanent deformations).
Another subject-matter of the invention is a process for the oxidation dyeing of keratinous fibres employing this composition.
The addition salts with an acid which can be used in the context of the dyeing compositions of the invention can in particular be chosen from hydrochlorides, hydrobromides, sulphates and tartrates.
Mention may more particularly be made, among the para-phenylenediamine derivatives of above formula (I), of 2-(xcex2-mesylaminoethyloxy)-para-phenylenediamine, 2-(xcex2-ureidoethyloxy)-para-phenylenediamine, 2-(xcex2-acetylaminoethyloxy)-para-phenylenediamine, 2-(xcex2-aminoethyloxy)-para-phenylenediamine and their addition salts with an acid.
Mention may more particularly be made, among the couplers of above formula (II), of meta-aminophenol, 5-amino-2-methoxyphenol, 5-amino-2-(xcex2-hydroxyethyloxy)phenol, 5-amino-2-methylphenol, 5-N-(xcex2-hydroxyethyl)amino-2-methylphenol, 5-N-(xcex3-hydroxypropyl)amino-2-methylphenol, 1,3-dihydroxybenzene, 2-methyl-1,3-dihydroxybenzene, 4-chloro-1,3-dihydroxybenzene and their addition salts with an acid.
The para-phenylenediamine derivative or derivatives of formula (I) in accordance with the invention and/or its or their addition salts with an acid preferably represent from 0.0005 to 10% by weight approximately of the total weight of the dyeing composition and more preferably still from 0.05 to 7% by weight approximately.
The coupler or couplers of formula (II) in accordance with the invention and/or its or their addition salts with an acid preferably represent from 0.0001 to 5% by weight approximately of the total weight of the dyeing composition and more preferably still from 0.005 to 3% by weight approximately.
The medium appropriate for dyeing (or vehicle) is generally composed of water or of a mixture of water and of at least one organic solvent, in order to dissolve the compounds which would not be sufficiently soluble in water. Mention may be made, for example, as organic solvent, of lower C1-C4 alkanols, such as ethanol and isopropanol; glycerol; glycols and glycol ethers, such as 2-butoxyethanol, propylene glycol, diethylene glycol monoethyl ether and diethylene glycol monomethyl ether, and aromatic alcohols, such as benzyl alcohol or phenoxyethanol, the analogous products and their mixtures.
The solvents can be present in proportions preferably of between 1 and 40% by weight approximately with respect to the total weight of the dyeing composition and more preferably still between 5 and 30% by weight approximately.
The pH of the dyeing composition as defined above is generally between 5 and 12 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents commonly used in dyeing keratinous fibres.
Mention may be made, among acidifying agents, by way of examples, of inorganic or organic acids, such as hydrochloric acid, orthophosphoric acid, carboxylic acids, such as tartaric acid, citric acid or lactic acid, or sulphonic acids.
Mention may be made, among basifying agents, by way of examples, of aqueous ammonia, alkaline carbonates, alkanolamines, such as mono-, di- and triethanolamines, and their derivatives, sodium hydroxide, potassium hydroxide and the compounds of following formula (III): 
in which R is a propylene residue optionally substituted by a hydroxyl group or a C1-C4 alkyl radical; and R5, R6, R7 and R8, which are identical or different, represent a hydrogen atom or a C1-C4 alkyl or C1-C4 hydroxyalkyl radical.
The dyeing composition in accordance with the invention can also comprise, in addition to the dyes defined above, other oxidation bases other than the para-phenylenediamine derivatives of formula (I) in accordance with the invention and/or other couplers other than the couplers of formula (II) in accordance with the invention and/or direct dyes, in particular for modifying the shades or enriching them with highlights.
The dyeing composition according to the invention can also include various adjuvants conventionally used in hair dyeing compositions, such as anionic, cationic, non-ionic or amphoteric surface-active agents or their mixtures, anionic, cationic, non-ionic or amphoteric polymers or their mixtures, inorganic or organic thickening agents, antioxidizing agents, penetration agents, sequestering agents, fragrances, buffers, dispersing agents, conditioning agents, such as, for example, silicones, film-forming agents, preserving agents or opacifying agents.
Of course, a person skilled in the art will take care to choose the optional additional compound or compounds mentioned above so that the advantageous properties intrinsically attached to the dyeing composition according to the invention are not, or not substantially, detrimentally affected by the envisaged addition or additions.
The dyeing composition according to the invention can be provided in various forms, such as in the form of liquids, creams or gels, or in any other form appropriate for carrying out dyeing of keratinous fibres and in particular of human hair.
Another subject-matter of the invention is a process for dyeing keratinous fibres and in particular human keratinous fibres, such as hair, employing the dyeing composition as defined above.
According to this process, the dyeing composition as defined above is applied to the fibres to be coloured, the colour being developed at acidic, neutral or alkaline pH using an oxidizing agent which is added only at the time of use to the dyeing composition or which is present in an oxidizing composition applied simultaneously or sequentially in a separate fashion.
According to a preferred embodiment of the invention, the pH resulting from the mixing of the dyeing composition and of the oxidizing composition is between 5 and 12 approximately.
According to a particularly preferred embodiment of the dyeing process according to the invention, the dyeing composition described above is mixed, at the time of use, with an oxidizing composition comprising, in a medium appropriate for dyeing, at least one oxidizing agent present in an amount sufficient to develop a colouring. The mixture obtained is subsequently applied to the keratinous fibres and is left to stand for 3 to 40 minutes approximately, preferably 5 to 30 minutes approximately, after which the hair is rinsed, washed with a shampoo, rinsed again and dried.
The oxidizing agent present in the oxidizing composition as defined above can be chosen from oxidizing agents conventionally used for the oxidation dyeing of keratinous fibres and among which may be mentioned hydrogen peroxide, urea hydrogen peroxide, alkali metal bromates, or persalts, such as perborates and persulphates. Hydrogen peroxide is particularly preferred.
The pH of the oxidizing composition including the oxidizing agent as defined above is such that, after mixing with the dyeing composition, the pH of the resulting composition applied to keratinous fibres preferably varies between 2 and 12 approximately and more preferably still between 5 and 11. It is adjusted to the desired value by means of acidifying or basifying agents commonly used in dyeing keratinous fibres and as defined above.
The oxidizing composition as defined above can also include various adjuvants conventionally used in hair dyeing compositions and as defined above.
The composition which is finally applied to keratinous fibres can be provided in various forms, such as in the form of liquids, creams or gels, or in any other form appropriate for carrying out dyeing of keratinous fibres and in particular of human hair.
Another subject-matter of the invention is a dyeing multi-compartment device or kit or any other packaging system with several compartments, a first compartment of which includes the dyeing composition as defined above and a second compartment of which includes the oxidizing composition as defined above. These devices can be equipped with a means allowing the desired mixture to be deposited on the hair, such as the devices disclosed in Patent FR-A-2,586,913 on behalf of the Applicant Company.
The examples which follow are intended to illustrate the invention without, for all that, limiting the scope thereof.